Nickel-catalyzed
aminoxylation of an unactivated C­(sp<sup>3</sup>)–H bond with
a stable nitroxyl radical has been accomplished
for the first time to offer various <i>N</i>-alkoxyamine
derivatives, which further enables a one-pot approach to α-formyl
acid derivatives. The aminoxylation process reported also provides
direct evidence for the oxidative addition of a cyclometallic intermediate
with a free radical, which is helpful for the reaction-mechanism study
in transition-metal-catalyzed functionalization of inert C­(sp<sup>3</sup>)–H bonds.